Surfactant-free cosmetic, dermatological and pharmaceutical agents

ABSTRACT

The invention relates to surfactant-free cosmetic, dermatological and pharmaceutical agents that contain at least one copolymer, obtainable by radical copolymerization of A) acryloyldimethyl taurine acid and/or acryloyldimethyl taurates, B) optionally one or more other olefinically unsaturated, non-cationic comonomers, C) optionally one or more olefinically unsaturated, cationic comonomers, D) optionally one or more silicon-containing component(s), E) optionally one or more fluorine-containing component(s), F) optionally one or more macromonomers, G) copolymerization optionally proceeding in the presence of at least one polymer additive, H) with the proviso that component A) is copolymerized with at least one component selected from groups D) to G).

[0001] The present invention relates to surfactant-free cosmetic,pharmaceutical, and dermatological compositions comprising combcopolymers based on acryloyldimethyltaurine.

[0002] The cosmetic or dermatological compositions in use at the presenttime mostly take the form of oil-in-water emulsions (i.e., a systemcomposed of a continuous aqueous phase and a discontinuous, dispersedoil phase) or of water-in-oil emulsions (i.e., a system composed of acontinuous, fat-containing phase and a discontinuous, dispersed aqueousphase).

[0003] The water-in-oil emulsions therefore include a continuous oilphase and allow a fatty film to form at the skin surface that preventstransepidermal water loss and protects the skin against externalaggressions. These emulsions are particularly suitable for protectingand enriching the skin and, in particular, for treating dry skin. Theoil-in-water emulsions, for their part, impart to the skin uponapplication a soft, less greasy and more gentle feel than thewater-in-oil emulsions.

[0004] The emulsions are generally stabilized by incorporation ofemulsifying surfactants of the oil-in-water (O/W) or water-in-oil (W/O)type which by virtue of their amphiphilic structure are located at theoil/water interface and so stabilize the dispersed droplets. It isgenerally necessary to add these surfactants in a considerable amount—upto 10% by weight with regard to the overall weight of the emulsion—inorder to obtain an appropriate stability.

[0005] These amphiphilic surfactants used in large quantity, however,may trigger an irritant effect toward the skin, eyes and/or scalp of theuser. Furthermore, their use at high concentrations may lead tocosmetically unwanted effects, such as a rough, sticky and/or viscoussensation, and may give rise to a compact, heavy substance. Furthermore,the surfactants have to be selected as a function of the polarity of theoils and are therefore compatible only with a limited number of oils,thereby acryloyidimethyltaurate-based thickener systems displayoutstanding properties in pH ranges below pH 6.0, i.e., within a pHrange in which it is no longer possible to operate with conventionalpoly(meth)acrylate thickeners.

[0006] A disadvantage of these acryloyldimethyltaurate-based thickenersystems, however, is that stable emulsions are generally only achievablein the presence of additional surfactant coemulsifiers.

[0007] There is therefore a need for surfactant-free cosmetic,decorative, and pharmaceutical compositions which are easy to prepare,possess outstanding rheological and sensorial properties and stability,and are stable particularly in the acidic pH range.

[0008] Surprisingly it has now been found that a new class of copolymersbased on acryloyidimethyltaurine (AMPS)—and suitable in the capacity ofa thickener, bodying agent, emulsifier, dispersant and/or stabilizer—areoutstandingly suitable for the formulation of acidic cosmetic,pharmaceutical, and dermatological compositions.

[0009] The invention accordingly provides surfactant-free cosmetic,dermatological, and pharmaceutical compositions comprising at least onecopolymer obtainable by free-radical copolymerization of

[0010] A) acryloyldimethyltau rine and/or acryloyidimethyltaurates,

[0011] B) if desired, one or more further olefinically unsaturated,noncationic, optionally crosslinking comonomers which have at least oneoxygen, nitrogen, sulfur or phosphorus atom and possess a molecularweight of less than 500 g/mol,

[0012] C) if desired, one or more olefinically unsaturated, cationiccomonomers which have at least one oxygen, nitrogen, sulfur orphosphorus atom and possess a molecular weight of less than 500 g/mol,

[0013] D) if desired, one or more silicon-containing components capableof free-radical polymerization and having a functionality of at leastone,

[0014] E) if desired, one or more fluorine-containing components capableof free-radical polymerization and having a functionality of at leastone,

[0015] F) if desired, one or more olefinically mono- or polyunsaturated,optionally crosslinking macromonomers each possessing at least oneoxygen, nitrogen, sulfur or phosphorus atom and having a number-averagemolecular weight of greater than or equal to 200 g/mol, themacromonomers not being a silicon-containing component D) orfluorine-containing component E),

[0016] G) the copolymerization taking place if desired in the presenceof at least one polymeric additive having number-average molecularweights of from 200 g/mol to 10⁹ g/mol,

[0017] H) with the proviso that component A) is copolymerized with atleast one component selected from one of the groups D) to G).

[0018] The copolymers of the invention preferably possess a molecularweight of from 10³ g/mol to 10⁹ g/mol, more preferably from 10⁴ to 10⁷g/mol, with particular preference from 5*10⁴ to 5*10⁶ g/mol.

[0019] The acryloyidimethyltaurates can be the organic or inorganicsalts of acryloyldimethyltaurine (acrylamidopropyl-2-methyl-2-sulfonicacid). Preference is given to the Li⁺, Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺, Al⁺⁺⁺and/orNH₄ ⁺ salts. Likewise preferred are the monoalkylammonium,dialkylammonium, trialkylammonium and/or tetraalkylammonium salts, inwhich the alkyl substituents of the amines may independently of oneanother be (C₁-C₂₂)-alkyl radicals or (C₂-C₁₀)-hydroxyalkyl radicals.Preference is also given to mono- to triethoxylated ammonium compoundswith different degrees of ethoxylation. It should be noted that mixturesof two or more of the abovementioned representatives are also embracedby the invention. The degree of neutralization of theacryloyldimethyltaurine can be between 0 and 100%, with particularpreference being given to a degree of neutralization of more than 80%.

[0020] Based on the total mass of the copolymers, the amount ofacryloyldimethyltaurine and/or acryloyldimethyltaurates is at least 0.1%by weight, preferably from 20 to 99.5% by weight, more preferably from50 to 98% by weight.

[0021] As comonomers B) it is possible to use all olefinicallyunsaturated noncationic monomers whose reaction parameters allowcopolymerization with acryloyl-dimethyltaurine and/oracryloyldimethyltaurates in the respective reaction media. Preferredcomonomers B) are unsaturated carboxylic acids and their anhydrides andsalts, and also their esters with aliphatic, olefinic, cycloaliphatic,arylaliphatic or aromatic alcohols having a carbon number of from 1 to30.

[0022] Particularly preferred unsaturated carboxylic acids are acrylicacid, methacrylic acid, styrenesulfonic acid, maleic acid, fumaric acid,crotonic acid, itaconic acid, and senecic acid.

[0023] Preferred counterions are Li⁺, Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺, Al⁺⁺⁺, NH₄ ⁺,monoalkyl-ammonium, dialkylammonium, trialkylammonium and/ortetraalkylammonium radicals, in which the alkyl substituents of theamines independently of one another can be (C₁-C₂₂)-alkyl radicals or(C₂-C₁₀)-hydroxyalkyl radicals. It is additionally possible to employmono- to triethoxylated ammonium compounds with a different degree ofethoxylation. The degree of neutralization of the carboxylic acids canbe between 0 and 100%.

[0024] Further preferred comonomers B) are open-chain N-vinyl amides,preferably N-vinylformamide (VIFA), N-vinylmethylformamide,N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyl lactams) with a ring size of 3 to 9, preferablyN-vinylpyrrolidone (NVP) and N-vinylcaprolactam; amides of acrylic andmethacrylic acid, preferably acrylamide, methacrylamide,N,N-dimethyl-acrylamide, N,N-diethylacrylamide, andN,N-diisopropylacrylamide; alkoxylated acrylamides and methacrylamides,preferably hydroxyethyl methacrylate, hydroxy- methylmethacrylamide, hydroxyethylmethacrylamide, hydroxypropylmethacryl-amide, and mono[2-(methacryloyloxy)ethyl] succinate; N,N-dimethylamino methacrylate;diethylaminomethyl methacrylate; acrylamido- and methacrylamido-glycolicacid; 2- and 4-vinylpyridine; vinyl acetate; glycidyl methacrylate;styrene; acrylonitrile; vinyl chloride; stearyl acrylate; laurylmethacrylate; vinylidene chloride; and/or tetrafluoroethylene.

[0025] Likewise suitable comonomers B) are inorganic acids and theirsalts and esters. Preferred acids are vinylphosphonic acid,vinylsulfonic acid, allylphosphonic acid, and methallylsulfonic acid.

[0026] The weight fraction of the comonomers B), based on the total massof the copolymers, can be from 0 to 99.8% by weight and is preferablyfrom 0.5 to 80% by weight, more preferably from 2 to 50% by weight.

[0027] Suitable comonomers C) include all olefinically unsaturatedmonomers with cationic charge which are capable of forming copolymerswith acryloyldimethyl-taurine or its salts in the chosen reaction media.The resulting distribution of the cationic charges across the chains canbe random, alternating, blocklike or gradientlike. It may be noted thatthe cationic comonomers C) also comprehend those which bear the cationiccharge in the form of a betaine, zwitterionic or amphoteric structure.

[0028] Comonomers C) for the purposes of the invention are alsoamino-functionalized precursors which can be converted bypolymer-analogous reactions into their corresponding quaternaryderivatives (e.g., reaction with dimethyl sulfate, methyl chloride),zwitterionic derivatives (e.g., reaction with hydrogen peroxide),betaine derivatives (e.g., reaction with chloroacetic acid), oramphoteric derivatives. Particularly preferred combnomers C) are

[0029] diallyldimethylammonium chloride (DADMAC),

[0030] [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MAPTAC),

[0031] [2-(acryloyloxy)ethyl]trimethylammonium chloride,

[0032] [2-methacrylamidoethyl]trimethylammonium chloride,

[0033] [2-(acrylamido)ethyl]trimethylammonium chloride,

[0034] N-methyl-2-vinylpyridinium chloride,

[0035] N-methyl-4-vinylpyridinium chloride,

[0036] dimethylaminoethyl methacrylate,

[0037] dimethylaminopropylmethacrylamide,

[0038] methacryloylethyl N-oxide and/or

[0039] methacryloylethylbetaine.

[0040] The weight fraction of the comonomers C), based on the total massof the copolymers, can be from 0.1 to 99.8% by weight, more preferablyfrom 0.5 to 30% by weight, and very preferably from 1 to 20% by weight.

[0041] Suitable polymerizable silicon-containing components D) are allcompounds which are olefinically at least monounsaturated and capable offree-radical copolymerization under the reaction conditions chosen ineach case. The distribution of the individual silicone-containingmonomers across the polymer chains which form need not necessarily berandom. The invention also embraces the formation, for example, ofblocklike (including multiblock) or gradientlike structures.Combinations of two or more different silicone-containingrepresentatives are also possible. The use of silicone-containingcomponents having two or more polymerization-active groups leads to theconstruction of branched or crosslinked structures.

[0042] Preferred silicone-containing components are those of formula(I).

R¹-Z-[(Si(R³R⁴)—O—)_(w)—(Si(R⁵R⁶)—O_(x)—]—R²  (I)

[0043] In this formula R¹ represents a polymerizable function from thegroup of the vinylically unsaturated compounds which is suitable for thesynthesis of polymeric structures by a free-radical route. R¹ representspreferably a vinyl, allyl, methallyl, methylvinyl, acryloyl(CH₂═CH—CO—), methacryloyl (CH₂=C[CH₃]—CO—), crotonyl, senecionyl,itaconyl, maleyl, fumaryl or styryl radical.

[0044] The attachment of the silicone-containing polymer chain to thereactive end group R¹ requires a suitable chemical bridge Z. Preferredbridges Z are —O—, ((C₁-C₅₀)alkylene), -((C₆-C₃₀)arylene)-,-((C₅-C₈)cycloalkylene)-, -((C₁-C₅₀)alkenylene)-, -(polypropyleneoxide)_(n)-, -(polyethylene oxide)_(o)-,-(polypropylene-oxide)_(n)(polyethylene oxide)_(o)-, where n and oindependently of one another denote numbers from 0 to 200 and thedistribution of the EO/PO units can be random or in the form of blocks.Further suitable bridge groups Z are -((C₁-C₁₀ )alkyl)-(Si(OCH₃)₂)- and-(Si(OCH₃)₂)-.

[0045] The polymeric central moiety is represented bysilicone-containing repeating units. The radicals R³, R⁴, R⁵, and R⁶denote independently of one another —CH₃, —O—CH₃, —C₆H₅ or —O—C₆H₅.

[0046] The indices w and x represent stoichiometric coefficients whichamount independently of one another to from 0 to 500, preferably 10 to250. The distribution of the repeating units across the chain can be notonly purely random but also blocklike, alternating or gradientlike.

[0047] R² can first be an aliphatic, olefinic, cycloaliphatic,arylaliphatic or aromatic (C₁ - C₅₀) hydrocarbon radical (linear orbranched) or —OH, —NH₂, —N(CH₃)₂, —R⁷ or stand for the structural unit[-Z—R¹]. The definition of the two variables Z and R¹ has already beenexplained. R⁷ stands for further Si-containing groups. Preferredradicals R⁷are —O—Si(CH₃)₃, —O—Si(Ph)₃, —O—Si(O—Si(CH₃)₃)₂CH₃) and—O—Si(O—Si(Ph)₃)₂Ph).

[0048] If R² is an element of the group [—Z—R¹] the monomers in questionare difunctional monomers which can be used to crosslink the polymerstructures which form. Formula (I) describes not onlysilicone-containing polymer species with vinylic functionalization and apolymer-typical distribution, but also defined compounds having discretemolecular weights.

[0049] Particularly preferred silicone-containing components are thefollowing components with acrylic or methacrylic modification:

[0050] methacryloyloxypropyldimethylsilyl-endblockedpolydimethylsiloxanes (f=2 to 500)

[0051] methacryloyloxypropyl-endblocked polydimethylsiloxanes (f=2 to500)

[0052] vinyldimethoxysilyl-endblocked polydimethylsiloxanes (f=2-500).

[0053] Based on the total mass of the copolymers, the amount ofsilicon-containing components can be up to 99.9% by weight, preferablyfrom 0.5 to 30% by weight, more preferably from 1 to 20% by weight.

[0054] Suitable polymerizable fluorine-containing components E) includeall compounds which are olefinically at least monounsaturated and whichare capable of free-radical copolymerization under the reactionconditions chosen in each case. The distribution of the individualfluorine-containing monomers across the polymer chains which form neednot necessarily be random. The invention also embraces the formation ofblocklike (including multiblock) or gradientlike structures, forexample. Combinations of two or more different fluorine-containingcomponents E) are also possible, it being clear to the expert thatmonofunctional representatives lead to the formation of comb-shapedstructures while di-, tri-, or polyfunctional components E) lead tostructures which are at least partly crosslinked.

[0055] Preferred fluorine-containing components E) are those of formula(II).

R¹—Y—C_(r)H_(2r)C_(s)F_(2s)CF₃   (II)

[0056] In this formula R¹ represents a polymerizable function from thegroup of the vinylically unsaturated compounds which is suitable for theconstruction of polymeric structures by a free-radical route. R¹ ispreferably a vinyl, allyl, methallyl, methylvinyl, acryloyl(CH₂═CH—CO—), methacryloyl (CH₂=C[CH₃]—CO—), crotonyl, senecionyl,itaconyl, maleyl, fumaryl or styryl radical, more preferably an acryloylor methacryloyl radical.

[0057] The attachment of the fluorine-containing group to the reactiveend group R¹ requires a suitable chemical bridge Y. Preferred bridges Yare —O—, —C(O)—, —C(O)—O—, —S—, —O—CH₂—CH (O—)—CH₂OH, —O—CH₂—CH(OH)—CH₂—O—, —O—SO₂—O—, —O—S(O)—O—, —PH—, —P(CH₃)-, —PO₃-, —NH—,—N(CH₃)-, —O—SO₂—O—, —O—phenyl—O—, —O—benzyl—O—,—O—(C₅-C₈)cycloalkyl—O—, —O—(C₁-C₅₀)alkenyl—O—,—O—(CH(CH₃)—(CH₂—O)_(n)—, —O—(CH₂-CH₂-O)_(n)—, and—O—([CH-CH₂—O]_(n—[CH) ₂—CH₂—O]_(m) _(o)-, where n, m, and oindependently of one another denote numbers from 0 to 200 and thedistribution of the EO and PO units can be random or in the form ofblocks. r and s are stoichiometric coefficients which independently ofone another denote numbers from 0 to 200.

[0058] Preferred fluorine-containing components E) of formula (II) are

[0059] perfluorohexylethanol methacrylate,

[0060] perfluorohexoylpropanol methacrylate,

[0061] perfluoroctylethanol methacrylate,

[0062] perfluoroctylpropanol methacrylate,

[0063] perfluorohexylethanolyl polyg lycol ether methacrylate,

[0064] perfluorohexoylpropanolyl poly[ethylg lycol-co-propylene g lycolether] acrylate,

[0065] perfluoroctylethanolyl poly[ethylglycol-block-co-propylene glycolether]

[0066] methacrylate,

[0067] perfluoroctylpropanolyl polypropylene glycol ether methacrylate.

[0068] Based on the total mass of the copolymer the amount offluorine-containing components can be up to 99.9% by weight, preferablyfrom 0.5 to 30% by weight, more preferably from 1 to 20% by weight.

[0069] The macromonomers F) are at least singly olefinicallyfunctionalized polymers having one or more discrete repeating units anda number-average molecular weight of greater than or equal to 200 g/mol.In the copolymerization it is also possible to use mixtures ofchemically different macromonomers F). The macromonomers are polymericstructures composed of one or more repeating units and have a molecularweight distribution characteristic of polymers.

[0070] Preferred macromonomers F) are compounds of formula (III).

R¹—Y—[(A)_(v)-(B)_(w)-(C)_(x)-(D)_(z)]—R²   (III)

[0071] R¹ represents a polymerizable function from the group of thevinylically unsaturated compounds which are suitable for constructingpolymeric structures by a free-radical route. Preferably R′ is a vinyl,allyl, methallyl, methylvinyl, acryloyl (CH₂═CH—CO—), methacryloyl(CH₂═C[CH₃]—CO—), crotonyl, senecionyl, itaconyl, maleyl, fumaryl orstyryl radical.

[0072] Attachment of the polymer chain to the reactive end grouprequires a suitable bridging group Y. Preferred bridges Y are —O—,—C(O)—, —C(O)—O—, —S—, —O—CH₂—CH(O—)—CH₂OH, —O—CH₂—CH(OH)—CH₂O—,—O—SO₂—O—, —O—SO₂—O—, —O—SO—O—, —PH—, —P(CH₃)—, —PO₃—, —NH—, and—N(CH₃)—, more preferably —O—. The polymeric central moiety of themacromonomer is represented by the discrete repeating units A, B, C, andD. Preferably the repeating units A, B, C, and D are derived from:acrylamide, methacrylamidq, ethylene oxide, propylene oxide, AMPS,acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile,maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene,diethylacrylamide, and diisopropylacrylamide.

[0073] The indices v, w, x, and z in formula (III) represent thestoichiometric coefficients relating to the repeating units A, B, C, andD. v, w, x, and z amount independently of one another to from 0 to 500,preferably 1 to 30, it being necessary for the sum of the fourcoefficients on average to be ≧1.

[0074] The distribution of the repeating units over the macromonomerchain can be random, blocklike, alternating or gradientlike.

[0075] R² denotes a linear or branched aliphatic, olefinic,cycloaliphatic, arylaliphatic or aromatic (C₁-C₅₀) hydrocarbon radical,OH, —NH₂, —N(CH₃)₂ or is the structural unit [—Y—R′].

[0076] In the case of R² being [—Y—R¹] the macromonomers in question aredifunctional and suitable for crosslinking the copolymers.

[0077] Particularly preferred macromonomers F) are acrylically ormethacrylically monofunctionalized alkyl ethoxylates of formula (IV).

[0078] R³, R⁴, R⁵, and R⁶ are independently of one another hydrogen orn-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic oraromatic (C₁-C₃₀) hydrocarbon radicals.

[0079] Preferably R³ and R⁴ are H or —CH₃, more preferably H; R⁵is H or—CH₃; and R⁶ is an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic,arylaliphatic or aromatic (C₁-C₃₀) hydrocarbon radical.

[0080] v and w are in turn the stoichiometric coefficients relating tothe ethylene oxide units (EO) and propylene oxide units (PO). v and wamount independently of one another to from 0 to 500, preferably 1 to30, it being necessary for the sum of v and w to be on average ≧1. Thedistribution of the EO and PO units over the macromonomer chain can berandom, blocklike, alternating or gradientlike. Y stands for theabovementioned bridges.

[0081] Further particularly preferred macromonomers F) have thefollowing structure in accordance with formula (IV): Name R³ R⁴ R⁵ R⁶ vw ® LA-030 H H —CH₃ -lauryl 3 0 methacrylate ® LA-070 H H —CH₃ -lauryl 70 methacrylate ® LA-200 H H —CH₃ -lauryl 20 0 methacrylate ® LA-250 H H—CH₃ -lauryl 25 0 methacrylate ® T-080 methacrylate H H —CH₃ -talc 8 0® T-080 acrylate H H H -talc 8 0 ® T-250 methacrylate H H —CH₃ -talc 250 ® T-250 crotonate —CH₃ H —CH₃ -talc 25 0 ® OC-030 H H —CH₃ -octyl 3 0methacrylate ® OC-105 H H —CH₃ -octyl 10 5 methacrytate ® Behenyl-010- HH H -behenyl 10 0 methylaryl ® Behenyl-020- H H H -behenyl 20 0methylaryl ® Behenyl-010- —CH₃ —CH₃ H -behenyl 10 0 senecionyl ® PEG-440diacrylate H H H -acryloyl 10 0 ® B-11-50 H H —CH₃ -butyl 17 13methacrylate ® MPEG-750 H H —CH₃ -methyl 18 0 methacrylate ® P-010acrylate H H H -phenyl 10 0 ® O-050-acrylate H H H -oleyl 5 0

[0082] Further particularly suitable macromonomers F) are esters of(meth)acrylic acid with

[0083] (C₁₀-C₁₈) fatty alcohol polyglycol ethers having 8 EO units(Genapol® C-080)

[0084] C₁₁ oxo alcohol polyglycol ethers having 8 EO units (Genapol®UD-080)

[0085] (C₁₂-C₁₄) fatty alcohol polyglycol ethers having 7 EO units(Genapol® LA-070)

[0086] (C₁₂-C₁₄) fatty alcohol polyglycol ethers having 11 EO units(Genapol® LA-110)

[0087] (C₁₆-C₁₈) fatty alcohol polyglycol ethers having 8 EO units(Genapol® T-080)

[0088] (C₁₆-C₁₈) fatty alcohol polyglycol ethers having 15 EO units(Genapol® T-150)

[0089] (C₁₆-C₁₈) fatty alcohol polyglycol ethers having 11 EO units(Genapol® T-110)

[0090] (C₁₆-C₁₈) fatty alcohol polyglycol ethers having 20 EO units(Genapol® T-200)

[0091] (C₁₆-C₁₈) fatty alcohol polyglycol ethers having 25 EO units(Genapol® T-250)

[0092] (C₁₈-C₂₂) fatty alcohol polyglycol ethers having 25 EO unitsand/or

[0093] iso-(C₁₆-C₁₈) fatty alcohol polyglycol ethers having 25 EO units.

[0094] The Genapol® grades are products of Clariant GmbH.

[0095] The molecular weight of the macromonomers F) is preferably from200 g/mol to 10⁶ g/mol, more preferably from 150 to 10⁴ g/mol, and verypreferably from 200 to 5 000 g/mol.

[0096] Based on the total mass of the copolymers it is possible for theamount of macromonomers to be up to 99.9% by weight. Preferred rangesused are from 0.5 to 30% by weight and from 70 to 99.5% by weight.Particularly preferred are ranges from 1 to 20% by weight and from 75 to95% by weight.

[0097] Preferred copolymers are those obtainable by copolymerizing atleast components A), C) and D).

[0098] Further preferred copolymers are those obtainable bycopolymerizing at least components A), C) and E).

[0099] Further preferred copolymers are those obtainable bycopolymerizing at least components A), C) and F).

[0100] Further preferred copolymers are those obtainable bycopolymerizing at least components A), D) and F).

[0101] Further preferred copolymers are those obtainable bycopolymerizing at least components A) and F).

[0102] Further preferred copolymers are those obtainable bycopolymerizing at least components A) and D).

[0103] Further preferred copolymers are those obtainable bycopolymerizing at least components A) and E).

[0104] In one preferred embodiment the copolymerization is conducted inthe presence of at least one polymeric additive G), the additive G)being added wholly or partly in solution to the polymerization mediumbefore the actual copolymerization. The use of two or more additives G)is likewise in accordance with the invention.

[0105] Crosslinked additives G) may likewise be used.

[0106] The additives G) or mixtures thereof must only be wholly orpartly soluble in the chosen polymerization medium. During the actualpolymerization step the additive G) has a number of functions. On theone hand it prevents the formation of overcrosslinked polymer fractionsin the copolymer which forms in the actual polymerization step, and onthe other hand the additive G) is statistically attacked by active freeradicals in accordance with the very well-known mechanism of graftcopolymerization. Depending on the particular additive G), this resultsin greater or lesser fractions of the additive being incorporated intothe copolymers. Moreover, suitable additives G) possess the property ofaltering the solution parameters of the copolymers which form during thefree-radical polymerization reaction in such a way that the averagemolecular weights are shifted to higher values. As compared withanalogous copolymers prepared without the addition of the additives G),those prepared with the addition of additives G) advantageously exhibita significantly higher viscosity in aqueous solution.

[0107] Preferred additives G) are homopolymers and copolymers which aresoluble in water and/or alcohols, preferably in t-butanol. The term“copolymers” also comprehends those having more than two differentmonomer types. Particularly preferred additives G) are homopolymers andcopolymers of N-vinyl-formamide, N-vinylacetamide, N-vinylpyrrolidone,ethylene oxide, propylene oxide, acryloyldimethyltaurine,N-vinylcaprolactam, N-vinylmethylacetamide, acrylamide, acrylic acid,methacrylic acid, N-vinylmorpholide, hydroxyethyl methacrylate,diallyidimethylammonium chloride (DADMAC) and/or[2-(methacryloyloxy)ethyl ]-trimethylammonium chloride (MAPTAC);polyalkylene glycols and/or alkylpolyglycols.

[0108] Particularly preferred additives G) are polyvinylpyrrolidones(e.g., Luviskol K15®, K20® and K30® from BASF), poly(N-vinylformamides),poly(N-vinylcaprolactams), and copolymers of N-vinylpyrrolidone,N-vinylformamide and/or acrylic acid, which may also have been partly orfully hydrolyzed.

[0109] The molecular weight of the additives G) is preferably from 10²to 10⁷ g/mol, more preferably from 0.5*104 to 106 g/mol.

[0110] The amount in which the polymeric additive G) is used, based onthe total mass of the monomers to be polymerized during thecopolymerization, is preferably from 0.1 to 90% by weight, morepreferably from 1 to 20% by weight, and with particular preference from1.5 to 10% by weight.

[0111] In another preferred embodiment the copolymers of the inventionare crosslinked, i.e., they contain comonomers having at least twopolymerizable vinyl groups.

[0112] Preferred crosslinkers are methylenebisacrylamide;methylenebismethacrylamide; esters of unsaturated monocarboxylic andpolycarboxylic acids with polyols, preferably diacrylates andtriacrylates, dimethacrylates and trimethacrylates, more preferablybutanediol and ethylene glycol diacrylate and methacrylate,trimethylolpropane triacrylate (TMPTA) and trimethylolpropanetrimethacrylate (TMPTMA); allyl compounds, preferably allyl(meth)acrylate, triallyl cyanurate, diallyl maleate, polyallyl esters,tetraallyloxyethane, triallylamine, tetraallylethylene-diamine; allylesters of phosphoric acid; and/or vinylphosphonic acid derivatives. Aparticularly preferred crosslinker is trimethylolpropane triacrylate(TMPTA). The weight fraction of crosslinking comonomers, based on thetotal mass of the copolymers, is preferably up to 20% by weight, morepreferably from 0.05 to 10% by weight, and very preferably from 0.1 to7% by weight.

[0113] The polymerization medium used may comprise all organic orinorganic solvents which have a very substantially inert behavior withrespect to free-radical polymerization reactions and whichadvantageously allow the formation of medium or high molecular weights.Those used preferably include water; lower alcohols; preferablymethanol, ethanol, propanols, iso-, sec- and t-butanol, very preferablyt-butanol; hydrocarbons having 1 to 30 carbon atoms, and mixtures of theaforementioned compounds.

[0114] The polymerization reaction takes place preferably in thetemperature range between 0 and 150° C., more preferably between 10 and100° C., either at atmospheric pressure or under elevated or reducedpressure. If desired the polymerization may also be performed under aninert gas atmosphere, preferably under nitrogen.

[0115] In order to initiate the polymerization it is possible to usehigh-energy electro-magnetic rays, mechanical energy, or the customarychemical polymerization initiators, such as organic peroxides, e.g.,benzoyl peroxide, tert-butyl hydro-peroxide, methyl ethyl ketoneperoxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators,such as azodiisobutyronitrile (AIBN), for example. Likewise suitable areinorganic peroxy compounds, such as (NH₄)₂S₂O₈, K₂S₂O₈ or H₂O₂, forexample, where appropriate in combination with reducing agents (e.g.,sodium hydrogensulfite, ascorbic acid, iron(ll) sulfate, etc.) or redoxsystems comprising as reducing component an aliphatic or aromaticsulfonic acid (e.g., benzenesulfonic acid, toluenesulfonic acid, etc.).

[0116] Serving as the polymerization medium may be any solvents whichare very substantially inert in respect of free-radical polymerizationreactions and which allow the development of high molecular weights. Useis preferably made of water and lower, tertiary alcohols or hydrocarbonshaving 3 to 30 carbon atoms. In one particularly preferred embodimentt-butanol is used as the reaction medium. Mixtures of two or morerepresentatives of the potential solvents described are of courselikewise in accordance with the invention. This also includes emulsionsof mutually immiscible solvents (e.g., water/hydrocarbons). Inprinciple, all kinds of reaction regime leading to the polymerstructures of the invention are suitable (solution polymerization,emulsion methods, precipitation methods, high-pressure methods,suspension methods, bulk polymerization, gel polymerization, and so on).Preferred suitability is possessed by precipitation polymerization,particularly preferred suitability by precipitation polymerization intert-butanol. The following list shows 67 copolymers suitable withparticular advantage for formulating the compositions of the invention.The different copolymers 1 to 67 are obtainable in accordance with thefollowing preparation processes 1, 2, 3, and 4.

[0117] Process 1:

[0118] These polymers can be prepared by the precipitation method intert-butanol. The monomers were introduced in t-butanol, the reactionmixture was rendered inert, and then, after initial heating to 60° C.,the reaction was initiated by addition of the correspondingt-butanol-soluble initiator (preferably dilauroyl peroxide). After theend of reaction (2 hours) the polymers were isolated by removal of thesolvent under suction and by subsequent vacuum drying.

[0119] Process 2:

[0120] These polymers are preparable by the gel polymerization method inwater. The monomers are dissolved in water, the reaction mixture isrendered inert, and then, after initial heating to 65° C., the reactionis initiated by addition of suitable initiators or initiator systems(preferably Na₂S₂O₈). The polymer gels are subsequently comminuted andthe polymers are isolated after drying.

[0121] Process 3:

[0122] These polymers are preparable by the emulsion method in water.The monomers are emulsified in a mixture of water/organ. solvent(preferably cyclohexane) using an emulsifier, the reaction mixture isrendered inert by means of N₂, and then, after initial heating to 80° C,the reaction is initiated by addition of suitable initiators orinitiator systems (preferably Na₂S₂O₈). The polymer emulsions aresubsequently evaporated down (with cyclohexane acting as an azeotropeformer for water) and the polymers are thereby isolated.

[0123] Process 4:

[0124] These polymers are preparable by the solution method in organicsolvents (preferably toluene, also, for example, tertiary alcohols). Themonomers are introduced in the solvent, the reaction mixture is renderedinert, and then, after initial heating to 70° C., the reaction isinitiated by addition of suitable initiators or initiator systems(preferably dilauroyl peroxide). The polymers are isolated byevaporating off the solvent and by subsequent vacuum drying.

[0125] Polymers having hydrophobic side chains, uncrosslinked No.Composition Preparation process 1 95 g AMPS 5 g Genapol T-080 1 2 90 gAMPS 10 g Genapol T-080 1 3 85 g AMPS 15 g Genapol T-080 1 4 80 g AMPS20 g Genapol T-080 1 5 70 g AMPS 30 g Genapol T-080 1 6 50 g AMPS 50 gGenapol T-080 3 7 40 g AMPS 60 g Genapol T-080 3 8 30 g AMPS 70 gGenapol T-080 3 9 20 g AMPS 80 g Genapol T-080 3 10 60 g AMPS 60 g BB104 11 80 g AMPS 20 g BB10 4 12 90 g AMPS 10 g BB10 3 13 80 g AMPS 20 gBB10 1 14 80 g AMPS 20 g Genapol LA040 1

[0126] Polymers having hydrophobic side chains, crosslinked PreparationNo. Composition process 15 80 g AMPS 20 g Genapol LA040 0.6 g AMA 1 1680 g AMPS 20 g Genapol LA040 0.8 g AMA 1 17 80 g AMPS 20 g Genapol LA0401.0 g AMA 1 18 628.73 g AMPS 120.45 g Genapol T-250 6.5 g 2 TMPTA 19 60g AMPS 40 g BB10 1.9 g TMPTA 4 20 80 g AMPS 20 g BB10 1.4 g TMPTA 4 2190 g AMPS 10 g BB10 1.9 g TMPTA 4 22 80 g AMPS 20 g BB10 1.9 g TMPTA 423 60 g AMPS 40 g BB10 1.4 g TMPTA 4

[0127] Polymers having hydrophobic side chains, crosslinked, graftedPrepa- ration No. Composition process 24 95 g AMPS 5 g BB10, 1.9 gTMPTA, 1 g Poly-NVP 1 25 90 g AMPS 10 g BB10, 1.9 g TMPTA, 1 g Poly-NVP1 26 85 g AMPS 15 g BB10, 1.9 g TMPTA, 1 g Poly-NVP 1 27 90 g AMPS 10 gBB10, 1.9 g TMPTA, 1 g Poly-NVP 1

[0128] Polymers having silicon-containing groups, uncrosslinked No.Composition Preparation process 28 80 g AMPS, 20 g Silvet 867 1 29 80 gAMPS, 50 g Silvet 867 4

[0129] Polymers having silicon-containing groups, crosslinked No.Composition Preparation process 30 80 g AMPS, 20 g Silvet 867, 0.5 g MBA4 31 80 g AMPS, 20 g Silvet 867, 1.0 g MBA 1 32 60 g AMPS, 40 g Y-12867,0.95 g AMA 1 33 80 g AMPS, 20 g Y-12867, 0.95 g AMA 1 34 90 g AMPS, 10 gY-12867, 0.95 g AMA 1 35 60 g AMPS, 40 g Silvet 7280, 0.95 g AMA 1 36 80g AMPS, 20 g Silvet 7280, 0.95 g AMA 1 37 90 g AMPS, 10 g Silvet 7280,0.95 g AMA 1 38 60 g AMPS, 40 g Silvet 7608, 0.95 g AMA 1 39 80 g AMPS,20 g Silvet 7608, 0.95 g AMA 1 40 90 g AMPS, 10 g Silvet 7608, 0.95 gAMA 1

[0130] Polymers having hydrophobic side chains and cationic groups,uncrosslinked Preparation No. Composition process 41 87.5 g AMPS, 7.5 gGenapol T-110, 5 g DADMAC 2 42 40 g AMPS, 10 g Genapol T110, 45 g 2methacrylamide 43 55 g AMPS, 40 g Genapol LA040, 5 g Quat 1 44 75 gAMPS, 10 g BB10, 6.7 g Quat 1

[0131] Polymers having hydrophobic side chains and cationic groups,crosslinked Preparation No. Composition process 45 60 g AMPS, 20 gGenapol T-80, 10 g Quat, 10 g 1 HEMA 46 75 g AMPS, 20 g Genapol T-250, 5g Quat, 1.4 g 1 TMPTA 47 75 g AMPS, 20 g Genapol T-250, 10 g Quat, 1.4 g1 TMPTA 48 75 g AMPS, 20 g Genapol T-250, 20 g Quat, 1.4 g 1 TMPTA

[0132] Polymers having fluorine-containing groups No. CompositionPreparation process 49 94 g AMPS, 2.02 g Fluowet AC 600 1 50 80 g AMPS,3 20 g perfluorooctylpolyethylene glycol methacrylate, 1 g Span 80

[0133] Polymers having fluorine-containing groups, grafted PreparationNo. Composition process 51 80 g AMPS, 10 g Fluowet AC 600, 5 g Poly-NVP1 52 70 g AMPS, 8 g perfluorooctylethyloxyglyceryl 4 methacrylate, 5 gPoly-NVP

[0134] Polyfunctionl polymers Preparation No. Composition process 53 80g AMPS, 10 g Genapol LA070, 10g Silvet 7608, 1.8 g TMPTA 1 54 70 g AMPS,5 g N-vinylpyrrolidone, 15 g Genapol T-250 4 methacrylate, 10 g Quat, 10g Poly-NVP 55 80 g AMPS, 5 g N-vinylformamide, 5 g Genapol O-150 2methacrylate, 10 g DADMAC, 1.8 g TMPTA, 8 g poly-N- vinylformamide 56 70g AMPS, 5 g N-vinylpyrrolidone, 15 g Genapol T- 1 250 methacrylate, 10 gQuat, 10 g Poly-NVP 57 60 g AMPS, 10 g Genapol-BE-020 methacrylate, 1 10g Genapol T-250 acrylate, 20 g Quat, 1 g Span 80 58 60 g AMPS, 20 gMPEG-750 methacrylate, 1 10 g methacryloyloxypropyldimethicone, 10 gperfluorooctylpolyethylene glycol methacrylate, 10 gpoly[N-vinylcaprolactone-co-acrylic acid] (10/90) 59 80 g AMPS, 5 gN-vinylformamide, 5 g Genapol O-150 1 methacrylate, 10 g DADMAC, 1.8 gTMPTA 60 70 g AMPS, 10 g Genapol T-250 acrylate, 5 g N-methyl- 14-vinylpyridinium chloride, 2.5 g Silvet Y-12867, 2.5 gperfluorohexylpolyethylene glycol methacrylate, 10 g polyethylene glycoldimethacrylate, 4 g poly[N-vinylcaprolactam] 61 10 g AMPS, 20 gacrylamide, 30 g N-2-vinylpyrrolidone, 3 20 g Silvet 7608, 10 gmethacryloyloxypropyldimethicone, 10 g Fluowet AC 812 62 60 g AMPS, 10 gDADMAC, 10 g Quat, 10 g Genapol-LA- 1 250 crotonate, 10 gmethacryloyloxypropyldimethicone, 7 g poly[acrylicacid-co-N-vinylformamide] 63 50 g AMPS, 45 g Silvet 7608, 1.8 g TMPTA, 18 g poly[N-vinylformamide] 64 20 g AMPS, 10 g Genapol T 110, 35 g MAA, 430 g HEMA, 5 g DADMAC 65 20 g AMPS, 80 g BB10, 1.4 g TMPTA 1 66 75 gAMPS, 20 g BB10, 6.7 g Quat, 1.4 g TMPTA 1 67 35 g AMPS, 60 gacrylamide, 2 g VIFA, 4 2.5 g vinylphosphonic acid, 2 mol % FluowetEA-600

[0135] Chemical designation of the reactants: AMPSacryloyldimethyltaurate, preferably Na or NH4 salt Genapol ® T-080C₁₆-C₁₈ fatty alcohol polyglycol ether having 8 EO units Genapol ® T-110C₁₂-C₁₄ fatty alcohol polyglycol ether having 11 EO units Genapol ®T-250 C₁₆-C₁₈ fatty alcohol polyglycol ether having 25 EO unitsGenapol ® LA-040 C₁₂-C₁₄ fatty alcohol polyglycol ether having 4 EOunits Genapol ® LA-070 C₁₂-C₁₄ fatty alcohol polyglycol ether having 7EO units Genapol ® O-150 C₁₆-C₁₈ fatty alcohol polyglycol methacrylateether methacrylate having 15 EO units, Genapol ® LA-250 C₁₂-C₁₄ fattyalcohol polyglycol crotonate ether crotonate having 25 EO unitsGenapol ® T-250 C₁₆-C₁₈ fatty alcohol polyglycol methacrylate ethermethacrylate having 25 EO units Genapol ® T-250 C₁₆-C₁₈ fatty alcoholpolyglycol acrylate ether acrylate having 25 EO units BB10 ®polyoxyethylene(10)behenyl ether TMPTA trimethylolpropane triacrylatePoly-NVP poly-N-vinylpyrrolidone Silvet ® 867 siloxane-polyalkyleneoxide copolymer MBA methylenebisacrylamide AMA allyl methacrylate®Y-12867 siloxane-polyalkylene oxide copolymer Silvet ® 7608polyalkylene oxide-modified heptamethyltrisiloxane Silvet ® 7280polyalkylene oxide-modified heptamethyltrisiloxane DADMACdiallyldimethylammonium chloride HEMA 2-hydroxyethyl methacrylate Quat2-(methacryloyloxy)ethyltrimethylammonium chloride Fluowet ® AC 600perfluoroalkylethyl acrylate Span ® 80 sorbitan ester

[0136] In one preferred embodiment the copolymers are water-soluble orwater-swellable. The acryloyidimethyltaurate comb copolymers describeddisplay advantageous properties in both crosslinked and noncrosslinkedform.

[0137] The described grafting of the acryloyidimethyltaurate combcopolymers with other polymers, which can be carried out optionally,leads to products having a particular polymer morphology and giving riseto optically clear gels in aqueous systems. A potential disadvantage ofthe copolymers without grafting is a more or less strong opalescence inaqueous solution. The basis for this opalescence is hithertounavoidable, overcrosslinked polymer fractions which arise in the courseof the synthesis and are inadequately swollen in water. This produceslight-scattering particles whose size is well above the wavelength ofvisible light and which are therefore the cause of the opalescence. Thedescribed grafting process, which can be carried out optionally,substantially reduces or entirely prevents the formation ofovercrosslinked polymer fractions in relation to conventionaltechniques.

[0138] The described incorporation both of cationic charges and ofsilicon, fluorine or phosphorus atoms into the acryloyidimethyltauratecomb copolymers, which can be carried out optionally, leads to productswhich in cosmetic formulations possess particular sensorial andrheological properties. An improvement in the sensorial and rheologicalproperties may be desired in particular in the context of use inrinse-off products (especially hair treatment compositions) or leave-onproducts (especially O/W emulsions).

[0139] Based on the finished compositions, the compositions of theinvention contain preferably from 0.01 to 10% by weight, more preferablyfrom 0.1 to 5% by weight, very preferably from 0.5 to 3% by weight, ofcopolymers.

[0140] The compositions of the invention may further comprise one ormore acidic organic active substances. Preferred compounds are thoseselected from glycolic acid, lactic acid, citric acid, tartaric acid,mandelic acid, salicylic acid, ascorbic acid, pyruvic acid,oligooxa-monocarboxylic and -dicarboxylic acids, alpha-hydroxy acids,fumaric acid, retinoic acid, sulfonic acids, benzoic acid, kojic acid,fruit acid, malic acid, gluconic acid, and derivatives thereof.

[0141] The formulations are normally adjusted to a pH in the range from2 to 12, preferably from 3 to 8.

[0142] The compositions can be on an aqueous or aqueous-alcoholic base,and examples include hair gels.

[0143] The compositions may further comprise emulsions and suspensionswhich comprise copolymers as thickeners, dispersants, emulsifiers,suspension media with a thickening effect, and bodying agents.

[0144] They may also be decorative preparations which contain solids andwhich comprise the copolymers as lubricants, adhesives, thickeners,dispersants, and emulsifiers.

[0145] The emulsifying, stabilizing and/or bodying effect of thecopolymers in emulsions is due to and/or boosted by association of thepolymer side chains with one another and also the interaction of thepolymer side chains with the hydrophobic oil components.

[0146] Besides a cosmetically and/or dermatologically acceptable aqueousmedium, the formulations may comprise organic solvents. These solventsare preferably selected from the group consisting of monohydric andpolyhydric alcohols, optionally ethoxylated polyethylene glycols,propylene glycol esters, sorbitol and its derivatives, glycol ethers,propylene glycol ethers, and fafty esters, and are used, based on thefinished compositions, at up to 90% by weight, preferably from 5 to 70%by weight.

[0147] The oil fraction of the emulsions is normally up to 95% byweight, preferably from 2 to 50% by weight, more preferably from 5 to20% by weight. The fraction of oily substances is dependent inter aliaon whether lotions, with a comparatively low viscosity, or creams andointments, of high viscosity, are to be prepared. The emulsions can beeither water-in-oil emulsions or oil-in-water emulsions.

[0148] The emulsions can be used as skincare compositions, such as daycreams, night creams, beauty creams, nutrient cream, body lotions,ointments and the like, for example, and as further auxiliaries andadditives may comprise cationic polymers, film formers, and also otheradditions customary in cosmetology, such as superfatting agents,moisturizing agents, stabilizers, active biogenic substances, glycerol,preservatives, pearlizing agents, dyes and fragrances, solvents,hydrotropic agents, opacifiers, further thickeners and dispersants, andalso protein derivatives such as gelatin, collagen hydrolysates, naturalor synthetic-based polypeptides, egg yolk, lecithin, lanolin and lanolinderivatives, deodorants, substances with a keratolytic and keratoplasticaction, enzymes and carrier substances, antioxidants, UV lightprotection filters, pigments and metal oxides, and antimicrobial agents.

[0149] An oily substance is any fatty substance which is liquid at roomtemperature (25° C.).

[0150] The fatty phase may therefore comprise one or more oils selectedpreferably from the following oils:

[0151] silicone oils, volatile or nonvolatile, linear, branched orcyclic, optionally with organic modification; phenylsilicones; siliconeresins and silicone gums; mineral oils such as paraffin oil or vaselineoil; oils of animal origin such as perhydrosqualene, lanolin; oils ofplant origin such as liquid triglycerides, e.g., sunflower oil, cornoil, soybean oil, rice oil, jojoba oil, babusscu oil, pumpkin oil,grapeseed oil, sesame oil, walnut oil, apricot oil, macadamia oil,avocado oil, sweet almond oil, lady's-smock oil, castor oil,triglycerides of caprylic/capric acids, olive oil, peanut oil, rapeseedoil, and coconut oil;

[0152] synthetic oils such as purcellin oil, isoparaffins, linear and/orbranched fatty alcohols and fatty acid esters, preferably guerbetalcohols having 6 to 18, preferably 8 to 10, carbon atoms; esters oflinear (C₆-C₁₃) fatty acids with linear (C₆-C₂₀) fatty alcohols; estersof branched (C₆-C₁₃) carboxylic acids with linear (C₆-C₂₀) fattyalcohols, esters of linear (C₆-C₁₈) fatty acids with branched alcohols,especially 2-ethylhexanol; esters of linear and/or branched fatty acidswith polyhydric alcohols (such as dimerdiol or trimerdiol, for example)and/or guerbet alcohols; triglycerides based on (C₆-C₁₀) fatty acids;

[0153] esters such as dioctyl adipate, diisopropyl dimer dilinoleate;propylene glycols/dicaprylate or waxes such as beeswax, paraffin wax ormicrowaxes, alone or in combination with hydrophilic waxes, such ascetylstearyl alcohol, for example; fluorinated and perfluorinated oils;fluorinated silicone oils; mixtures of the aforementioned compounds.

[0154] Suitable nonionogenic coemulsifiers include adducts of from 0 to30 mol of ethylene oxide and/or from 0 to 5 mol of propylene oxide withlinear fatty alcohols having 8 to 22 carbon atoms, with fatty acidshaving 12 to 22 carbon atoms, with alkylphenols having 8 to 15 carbonatoms in the alkyl group, and with sorbitan or sorbitol esters;(C₁₂-C₁₈) fatty acid monoesters and diesters of adducts of from 0 to 30mol of ethylene oxide with glycerol; glycerol monoesters and diestersand sorbitan monoesters and diesters of saturated and unsaturated fattyacids having 6 to 22 carbon atoms and, where appropriate, their ethyleneoxide adducts; adducts of from 15 to 60 mol of ethylene oxide withcastor oil and/or hydrogenated castor oil; polyol esters and especiallypolyglycerol esters, such as polyglyceryl polyricinoleate andpolyglyceryl poly-12-hydroxystearate, for example. Likewise suitable aremixtures of compounds from one or more of these classes of substance.

[0155] Suitable cationic polymers include those known under the INCIdesignation “Polyquaternium”, especially Polyquaternium-31,Polyquaternium-16, Polyquaternium-24, Polyquaternium-7,Polyquaternium-22, Polyquaternium-39, Polyquaternium-28,Polyquaternium-2, Polyquaternium-10, Polyquaternium-11, and alsoPolyquaternium 37&mineral oil&PPG trideceth (Salcare SC95),PVP-dimethylaminoethyl methacrylate copolymer,guar-hydroxypropyltriammonium chlorides, and also calcium alginate andammonium alginate. It is additionally possible to employ cationiccellulose derivatives; cationic starch; copolymers of diallylammoniumsalts and acrylamides; quaternized vinylpyrrolidone/vinylimidazolepolymers; condensation products of polyglycols and amines; quaternizedcollagen polypeptides; quaternized wheat polypeptides;polyethyleneimines; cationic silicone polymers, such as amidomethicones,for example; copolymers of adipic acid anddimethylaminohydroxypropyldiethylenetriamine; polyaminopolyamide andcationic chitin derivatives, such as chitosan, for example.

[0156] Examples of suitable silicone compounds are dimethylpolysiloxane,methylphenylpolysiloxanes, cyclic silicones, and amino-, fatty acid-,alcohol-, polyether-, epoxy-, fluoro- and/or alkyl-modified siliconecompounds, and also polyalkylsiloxanes, polyalkylarylsiloxanes,polyethersiloxanes, as described in U.S. Pat. No. 5,104,645 and thedocuments cited therein, which at room temperature may be present eitherin liquid form or in resin form.

[0157] Suitable film formers, depending on the intended application,include water-soluble polyurethanes, for example, C₁₀-polycarbamylpolyglyceryl esters, polyvinyl alcohol, polyvinylpyrrolidone, copolymersthereof, for exariple vinylpyrrolidone/vinyl acetate copolymers,water-soluble acrylic acid copolymers and their esters or salts,examples being partial ester copolymers of acrylic/methacrylic acid andpolyethylene glycol ethers of fatty alcohols, such asacrylate/steareth-20 methacrylate copolymers, water-soluble cellulose,examples being hydroxymethylcellulose, hydroxyethylcellulose,hydroxypropylcellulose, water-soluble quaterniums, polyquaterniums,carboxyvinyl polymers, such as carbomers and their salts,polysaccharides, polydextrose for example, and glucan.

[0158] As superfatting agents it is possible to use substances such as,for example, polyethoxylated lanolin derivatives, lecithin derivatives,polyol fatty acid esters, monoglycerides, and fatty acid alkanol amides,the latter serving simultaneously as foam stabilizers. Moisturizersavailable include for example isopropyl palmitate, glycerol and/orsorbitol.

[0159] As stabilizers it is possible to use metal salts of fatty acids,such as magnesium, aluminum and/or zinc stearate, for example.

[0160] Active biogenic substances are to be understood as including, forexample, plant extracts and vitamin complexes.

[0161] The compositions of the invention can be blended withconventional ceramides, pseudoceramides, fatty acidN-alkylpolyhydroxyalkyl amides, cholesterol, cholesterol fatty acidesters, fatty acids, triglycerides, cerebrosides, phospholipids, andsimilar substances as a care additive.

[0162] Suitable UV filters include for example 4-aminobenzoic acid;

[0163] 3-(4′-trimethyl-ammonium)benzylideneboran-2-one methylsulfate;3,3, 5-trimethylcyclohexyl salicylate; 2-hydroxy-4-methoxybenzophenone;2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium, andtriethanolamine salts;

[0164] 3,3′-(1,4-phenylene-dimethine)bis(7,7-dimethyl-2-oxobicyclo[2.2.1 ]heptane-1-methanesulfonic acidand its salts;1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione;

[0165] 3-(4′-sulfo)benzylidenebornan-2-one and its salts; 2-ethylhexyl2-cyano-3,3-diphenylacrylate; polymer of N-[2(and4)-(2-oxoborn-3-ylidenemethyl)benzyl ]-acrylamide; 2-ethylhexyl4-methoxycinnamate; ethoxylated ethyl 4-aminobenzoate; isoamyl4-methoxycinnamate; 2,4,6-tris[p-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine;

[0166]2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)propyl)phenol;

[0167] 4,4′-[(6-[4-((1,1 -dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazin-2,4-yl)diimino]bis(benzoicacid 2-ethylhexyl ester);

[0168] 3-(4′-methylbenzylidene)-D,L-camphor; 3-benzylidenecamphor;2-ethylhexyl salicylate; 2-ethylhexyl 4-d imethylaminobenzoate;hydroxy-4-methoxybenzo-phenone-5-sulfonic acid (sulisobenzone) and thesodium salt; and/or 4-isopropyl-benzyl salicylate.

[0169] As pigments/micropigments it is possible for example to usemicrofine titanium dioxide, mica-titanium oxide, iron oxides, mica-ironoxide, zinc oxide, silicon oxides, ultramarine blue, and chromiumoxides.

[0170] Examples of suitable antioxidants include superoxide dismutase,tocopherol (vitamin E), and ascorbic acid (vitamin C).

[0171] Examples of suitable preservatives include phenoxyethanol,parabens, pentanediol or sorbic acid.

[0172] As dyes it is possible to use the substances which are suitableand approved for cosmetic purposes.

[0173] Suitable active antifungal substances (fungicides) includepreferably ketoconazole, oxiconazole, bifonazole, butoconazole,cloconazole, clotrimazole, econazole, enilconazole, fenticonazole,isoconazole, miconazole, sulconazole, tioconazole, fluconazole,itraconazole, terconazole, naftifine and terbinafine, Zn pyrithione, andoctopirox.

[0174] Essential to the invention is that the describedacryloyldimethyltaurate copolymers can be used even in the absence of anadditional nonsurfactant coemulsifier (e.g., polymeric emulsifiers)and/or in the absence of an additional bodying agent. The presence ofnonsurfactant coemulsifiers and/or bodying agents is therefore notmandatory, though is possible. Combination with other knownnonsurfactant coemulsifiers and/or bodying agents may be desirable inorder to set specific cosmetic profiles and to exploit synergisticeffects.

[0175] The qualities achieved are extremely innovative: the emulsionsare creamy and ointmentlike and above all do not have the gellike oreven gelatinelike appearance of certain prior art emulsions in which theexternal aqueous phase is thickened. The cosmetic feel on the skin isalso very good. Upon application the emulsion imparts a sensation offreshness and of comfort, and at the same time has a rich and nourishingeffect; it is soft and luxurious and in no way sticky. Emulsions of theinvention can be prepared in a conventional manner, by hot,hot-hot/cold, or PIT emulsification, for example.

[0176] The examples which follow are intended to illustrate theinvention, though without restricting it thereto (the percentages are byweight). The copolymers used in the examples are representatives of theparticularly preferred copolymers 1 to 67 already listed in thedescription. They were prepared by the therein-indicated processes 1, 2,3 or 4 using the preferred initiators and solvents.

EXAMPLE 1

[0177] O/W skin milk with keratolytic effect, surfactant-free

[0178] Composition A Copolymer No. 15  1.0% Mineral oil 4.00% Almond oil4.00% ®Cetiol SN (Henkel) 8.00% Cetearyl isononanoate B ®Aristoflex AVC(Clariant) 0.30% Ammonium acryloyldimethyltaurate/ VP copolymer C Waterad 100%   Citric acid 0.30% Malic acid 0.40% Glycolic acid 0.70% Lacticacid 0.70% D Fragrances 0.30%

[0179] Preparation I Mix A and B. II Mix the components C. III Add II toI. II Stir D into I. III Homogenize emulsion, pH 3.5.

EXAMPLE 2

[0180] Surfactant-free moisturizing lotion A Almond oil 7.00%Cyclomethicone 5.00% B Copolymer No. 18 1.50% C Glycerol 7.00% Water ad100%   Preservative q.s. D Fragrance 0.30%

[0181] Preparation I Mix A and B. II Stir solution of C into I. III AddD to II. IV Homogenize. V pH 5.5.

EXAMPLE 3

[0182] Refreshing, surfactant-free lotion A Almond oil 7.00%Cyclomethicone 5.00% B Copolymer No. 32 1.50% C Glycerol 3.00% Ethanol20.00%  Water ad 100%   Preservative q.s. D Fragrance 0.30%

[0183] Preparation I Mix A and B. II Stir solution of C into I. III AddD to II. IV Homogenize.

EXAMPLE 4

[0184] Surfactant-free lotion with refreshing, vivifying effect A Jojobaoil 5.00% Almond oil 3.00% Cetiol V 3.00% Decyl oleate B Copolymer No.35 1.50% C Glycerol 3.00% Menthol 0.70% Camphor 0.30% Ethanol 5.00%Water ad 100%   Preservative q.s. D Fragrance 0.30%

[0185] Preparation I Mix A and B. II Stir solution of C into I. III AddD to II. IV Homogenize. V Adjust pH to 6.00.

What is claimed is:
 1. A surfactant-free cosmetic, dermatological orpharmaceutical composition which comprises at least one copolymerobtainable by free-radical copolymerization of A)acryloyldimethyltaurine and/or acryloyldimethyltaurates, B) if desired,one or more further olefinically unsaturated, noncationic, optionallycrosslinking comonomers which have at least one oxygen, nitrogen, sulfuror phosphorus atom and possess a molecular weight of less than 500g/mol, C) if desired, one or more olefinically unsaturated, cationiccomonomers which have at least one oxygen, nitrogen, sulfur orphosphorus atom and possess a molecular weight of less than 500 g/mol,D) one or more silicon-containing components capable of free-radicalpolymerization and having a functibnality of at least one, where atleast one silicon-containing component is a compound selected from theformulae

in which f=2 to 500,

in which f=2 to 500, and

in which f=2-500, E) if desired, one or more fluorine-containingcomponents capable of free-radical polymerization and having afunctionality of at least one, F) if desired, one or more olefinicallymono- or polyunsaturated, optionally crosslinking macromonomers eachpossessing at least one oxygen, nitrogen, sulfur or phosphorus atom andhaving a number-average molecular weight of greater than or equal to 200g/mol, the macromonomers not being a silicon-containing component D) orfluorine-containing component E), G) the copolymerization taking placeIf desired in the presence of at least one polymeric additive havingnumber-average molecular weights of from 200 g/mol to 10⁹ g/mol.
 2. Acomposition as claimed in claim 1, wherein the comonomers B) areunsaturated carboxylic acids, salts of unsaturated carboxylic acids,anhydrides of unsaturated carboxylic acids, esters of unsaturatedcarboxylic acids with aliphatic, olefinic, cycloaliphatic, arylaliphaticor aromatic alcohols having 1 to 22 carbon atoms, open-chain N-vinylamides, cyclic N-vinyl amides having a ring size of from 3 to 9, amidesof acrylic acid, amides of methacrylic acid, amides of substitutedacrylic acids, amides of substituted methacrylic acids, 2-vinylpyridine,4-vinyl-pyridine, vinyl acetate; styrene, acrylonitrile, vinyl chloride,vinylidene chloride, tetrafluoroethylene, vinylphosphonic acid or theesters or salts thereof, vinylsulfonic acid or the esters or saltsthereof, allylphosphonic acid or the esters or salts thereof and/ormethallylsulfonic acid or the esters or salts thereof.
 3. A compositionas claimed in claim 1 and/or 2, wherein the comonomers C) arediallyldimethylammonium chloride (DADMAC),[2-(methacryloyloxy)ethyl]trimethylammonium chloride (MAPTAC),[2-(acryloyloxy)ethyl]trimethylammonium chloride,[2-methacrylamidoethyl]trimethylammonium chloride,[2-(acrylamido)ethyl]trimethylammonium chloride,N-methyl-2-vinylpyridinium chloride, N-methyl-4-vinylpyridiniumchloride, dimethylaminoethyl methacrylate,dimethylaminopropylmethacrylamide, methacryloylethyl N-oxide and/ormethacryloylethylbetaine.
 4. A composition as claimed in at least one ofclaims 1 to 3, wherein the silicon-containing components D) arecompounds of the formula (I) R¹-Z-[(Si(R³R⁴)—O—)_(w)(Si(R⁵R⁶)—O)_(x)]—R²  (I) where R¹ represents a vinyl, allyi, methallyl, methylvinyl,acryloyl, methacryloyl, crotonyl, senecionyl, itaconyl, maleyl, fumarylor styryl radical; Z is a chemical bridge, preferably selected from —O',-((C₁-C₅₀)alkylene)-, ((C₆-C₃₀)arylene)-, -((C₅-C₈)cycloalkylene)-,-((C₁-C₅₀)alkenylene)-, -(polypropylene oxide)_(n)-, -(polyethyleneoxide)_(o)-, -(polypropylene oxide)n(polyethylene oxide)_(o)-, where nand o independently of one another denote numbers from 0 to 200, and thedistribution of the EO/PO units can be random or in the form of blocks,-((C₁-C₁₀)alkyl)—(Si(OCH₃)₂)- and —(Si(OCH₃)₂)-; R³, R⁴, R⁵, and R⁶independently of one another are —CH₃, —O—CH₃, —C₆H₅ or —O—C₆H₅; w, xdenote numbers from 0 to 500, it being necessary for either w or x to begreater than zero, and R² is a saturated or unsaturated aliphatic,cycloaliphatic, arylaliphatic or aromatic radical having in each case 1to 50 carbon atoms or a group of the formulae —OH, —NH₂, —N(CH₃)₂, —R⁷or a group -Z—R¹, where Z and R¹ have the meanings mentioned above, andR⁷ is a group of the formula —O—Si(CH₃)₃, —O—Si(phenyl)₃,—O—Si(O—Si(CH₃)₃)₂CH₃) and —O—Si(O—Si(Ph)₃)₂Ph).
 5. A composition asclaimed in at least one of claims 1 to 4, wherein thefluorine-containing components E) are compounds of the formula (II)R¹—Y—C_(r)H_(2r)C_(s)F_(2s)CF₃   (II) where R¹ represents apolymerizable function from the group of the vinylically unsaturatedcompounds, preferably a vinyl, allyl, methallyl, methylvinyl, acryloyl,methacryloyl, crotonyl, senecionyl, itaconyl, maleyl, fumaryl or styrylradical; Y is a chemical bridge, preferably —O—, —C(O)—, —C(O)—O—, —S—,—O—CH₂—CH(O—)—CH₂OH, —O—CH₂—OH (OH)—CH₂—O—, —O—SO₂—O—, —O—S(O)—O—, —PH—,—P(CH₃)—, —PO₃—, —NH—, —N(CH₃)-, —O—(C₁-C₅₀)alkyl—O—, —O—phenyl—O—,—O—benzyl—O—, —O—(C₅-C₈)cycloalkyl—O—, —O—(C₁-C₅₀)alkenyl—O—, —O—(CH(CH₃)—CH₂—O)_(n)-, —O—(CH₂-C H₂—O)_(n)-, and—O—([CH-CH₂—O]_(n)-[CH₂-CH₂—O]_(m))_(o)-, where n, m, and oindependently of one another denote numbers from 0 to 200, and r, s arestoichiometric coefficients which independently of one another arenumbers between 0 and
 200. 6. A composition as claimed in at least oneof claims 1 to 5, wherein the macromonomers F) are compounds of theformula (III) R¹ —Y—[(A)_(v)-(B)_(w)-(C)_(x)-(D)_(z)]—R²   (III) whereR¹ represents a polymerizable function from the group of the vinylicallyunsaturated compounds, preferably a vinyl, allyl, methalyl, methylvinyl,acryloyl, methacryloyl, crotonyl, senecionyl, itaconyl, maleyl, fumarylor styryl radical; Y is a bridging group, preferably —O—, —S—, —C(O)—,—C(O)—O—, —O—CH₂—CH(O—)—CH₂OH, —O—CH₂—CH (OH)—CH₂O—, —O—SO₂—O—,—O—SO₂—O—, —O—SO—O—, —PH—, —P(CH₃)—, —PO₃—, —NH—, and —N(CH₃)-; A, B, C,and D independently of one another are discrete chemical repeatingunits, preferably originating from acrylamide, methacrylamide, ethyleneoxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methylmethacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene,1,3-butadiene, isoprene, isobutene, diethylacrylamide, anddiisopropylacrylamide, more preferably ethylene oxide or propyleneoxide; v, w, x, and z independently of one another amount to from 0 to500, preferably from 1 to 30, the sum of v, w, x, and z being on average≧1; and R² is a linear or branched aliphatic, olefinic, cycloaliphatic,arylaliphatic or aromatic (C₁-C₅₀) hydrocarbon radical, OH, —NH₂ or—N(CH₃)₂ or is [—Y—R¹].
 7. A composition as claimed in at least one ofclaims 1 to 6, wherein the polymeric additives G) are homopolymers orcopolymers of N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone,ethylene oxide, propylene oxide, acryloyl-dimethyltaurine,N-vinylcaprolactam, N-vinylmethylacetamide, acrylamide, acrylic acid,methacrylic acid, N-vinylmorpholide, hydroxymethyl methacrylate,diallyl-dimethylammonium chloride (DADMAC) and/or[2-(methacryloyloxy)ethyl ]trimethyl-ammonium chloride (MAPTAC);polyalkylene glycols and/or alkylpolyglycols.
 8. A composition asclaimed in at least one of claims 1 to 7, wherein the copolymerizationtakes place in the presence of at least one polymeric additive G).
 9. Acomposition as claimed in at least one of claims 1 to 8, wherein thecopolymers are crosslinked.
 10. A composition as claimed in at least oneof claims 1 to 9, wherein the copolymers are prepared by precipitationpolymerization in tert-butanol.
 11. A composition as claimed in at leastone of claims 1 to 10, wherein the copolymers are water-soluble orwater-swellable.
 12. A composition as claimed in at least one of claims1 to 11, which comprises, based on the finished composition, from 0.01to 10% by weight of the copolymers.
 13. A composition as claimed in atleast one of claims 1 to 12, which has a pH of from 2 to
 12. 14. Acomposition as claimed in at least one of claims 1 to 13, containing upto 70% by weight of organic solvents.
 15. A composition as claimed inclaim 14, wherein the organic solvents are selected from monohydric andpolyhydric alcohols, optionally ethoxylated polyethylene glycols,propylene glycol esters, sorbitol and its derivatives, glycol ethersand/or propylene glycol ethers.
 16. A composition as claimed in at leastone of claims 1 to 15, containing, based on the finished composition, upto 95% by weight, preferably from 2 to 50% by weight, of oil phase. 17.A composition as claimed in claim 16, wherein the oil phase comprisesone or more oils selected from silicone oils, phenylsilicones, siliconeresins, silicone gums, mineral oils, paraffin oils, vaseline oil, oilsof animal origin, oils of plant origin, synthetic oils, linear and/orbranched fatty alcohols and fatty acid esters, waxes, fluorinated oilsand/or perfluorinated oils.
 18. A composition as claimed in at least oneof claims 1 to 17, which is an emulsion or suspension.